US6136914A - Anionic polymerization initiators for preparing macro-branched diene rubbers - Google Patents

Anionic polymerization initiators for preparing macro-branched diene rubbers Download PDF

Info

Publication number
US6136914A
US6136914A US09/042,096 US4209698A US6136914A US 6136914 A US6136914 A US 6136914A US 4209698 A US4209698 A US 4209698A US 6136914 A US6136914 A US 6136914A
Authority
US
United States
Prior art keywords
polymer
particle
alkali metal
polymers
atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US09/042,096
Other languages
English (en)
Inventor
William L. Hergenrother
William M. Cole
Theodore J. Knutson
Georg G. A. Bohm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bridgestone Corp
Original Assignee
Bridgestone Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bridgestone Corp filed Critical Bridgestone Corp
Assigned to BRIDGESTONE CORPORATION reassignment BRIDGESTONE CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KNUTSON, THEODORE J., BOHM, GEORG G.A., COLE, WILLIAM M., HERGENROTHER, WILLIAM L.
Priority to US09/042,096 priority Critical patent/US6136914A/en
Priority to EP99103963A priority patent/EP0942004A3/fr
Priority to CA002265238A priority patent/CA2265238A1/fr
Priority to JP11064984A priority patent/JPH11315108A/ja
Priority to ARP990101094A priority patent/AR018748A1/es
Priority to BR9902331-8A priority patent/BR9902331A/pt
Priority to US09/569,253 priority patent/US6271314B1/en
Publication of US6136914A publication Critical patent/US6136914A/en
Application granted granted Critical
Priority to US09/852,507 priority patent/US6384150B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • C08F4/027—Polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/46—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T152/00—Resilient tires and wheels
    • Y10T152/10—Tires, resilient

Definitions

  • the invention relates to anionic polymerization resulting in very high molecular weight, highly branched diene polymers. More particularly, the invention relates to novel multiply-metalated, solid supported anionic polymerization initiators that are useful for producing such polymers.
  • the macro-branched polymers synthesized by the process of the invention exhibit desirable properties, such as the ability to absorb hydrocarbon solvents and oils, and are readily compounded to form vulcanizable elastomeric compounds and articles that have excellent resistance to wear and tear and exhibit reduced hysteresis properties.
  • Anionic polymerization initiators based on lithium are well known for producing linear polydiene homopolymers and copolymers.
  • Lithium-based macrocyclic anionic polymerization initiators have also been described in U.S. Pat. Nos. 5,677,399 and 5,700,888. These initiators are utilized to form stable macrocyclic polymers that have low viscosities at high molecular weights and thus provide for enhanced polymer processibility during molding, extruding and the forming of films.
  • Such polymers can be compounded to form vulcanizable elastomeric compounds and articles that exhibit reduced hysteresis properties.
  • anionic polymerization initiators that can be used to synthesize high molecular weight linear polymers that are easily processible and have the desirable properties described above.
  • the present invention provides novel solid supported anionic polymerization initiators that are multiply metalated and are useful for producing extremely high molecular weight branched diene polymers.
  • an advantage of the invention is that the macro-branched diene polymers are prepared using the invention initiators under normal conditions for an anionic polymerization process while the initiators are in suspension in a solution of monomers.
  • the initiators of the present invention are also suitable for use in gas phase anionic polymerization of conjugated diene monomers, as disclosed in our co-pending, co-assigned U.S. patent application, Ser. No. 09/041/719, now allowed, the disclosure of which is hereby incorporated by reference.
  • the polymers produced by anionic polymerization employing the invention initiators are useful for producing many different high performance vulcanates.
  • the macro-branched polymers synthesized by the process of the invention also exhibit other desirable properties, such as the ability to readily absorb hydrocarbon solvents and oils, and they are easily compounded to form vulcanizable elastomeric compounds and articles that have excellent resistance to wear and tear and exhibit reduced hysteresis properties.
  • the anionic polymerization initiators of the invention have the formula P(Me) n , wherein P is a metalatable particle having a diameter of about 1 micron to about 1000 microns comprising a thermoplastic polymer or a cured elastomer.
  • the particle is multiply-metalated with a Group IA alkali metal (Me).
  • the alkali metal atoms bonded to a single particle may all be the same or may be different from each other.
  • the metal atoms may be any Group IA alkali metal including lithium, sodium, potassium, rubidium, cesium and francium.
  • the metal atoms are selected from lithium, sodium and potassium and, more preferably, are a mixture of lithium atoms and at least one of sodium atoms and potassium atoms. Most preferably, all of the alkali metal atoms are the same and are lithium atoms.
  • metalated refers to an acid:base reaction, known to those skilled in the art, involving the transfer of a metal atom from a strong base to a more acidic polymer with the concomitant transfer of a hydrogen atom from the polymer to the base, thus forming a polymer carbon-metal covalent bond.
  • a "metalatable" thermoplastic polymer or cured elastomer is one that can participate in this reaction and become metalated.
  • anionic polymerization initiators are used to homopolymerize conjugated diolefin monomers having from about 4 to about 12 carbon atoms, and to copolymerize the conjugated diolefin monomers with monovinyl aromatic monomers having from about 8 to about 20 carbon atoms, to prepare a macro-branched diene homopolymer or copolymer having the formula
  • polymer represents a polymer chain covalently bonded to the particle.
  • the polymerization reaction is terminated with a terminating or a functionalizing agent.
  • the resulting polymers have a low T g , preferably less than -20° C., more preferably less than -30° C., and most preferably less than -35° C., and are readily usable in rubber products such as tires.
  • the invention provides the initiators, the macro-branched diene polymer, a vulcanizable elastomer composition formed from the polymer, and a tire having at least one component formed from the vulcanizable elastomer composition.
  • the vulcanizable elastomer composition may comprise the invention polymer only or may comprise a blend of the invention polymer and at least one other polymer, such as styrene-butadiene rubber, natural rubber, polyisoprene, poly-(ethylene propylene diene monomer), and the like.
  • the invention further provides a method for preparing the anionic polymerization initiators described above, comprising the step of reacting (i) an alkali metal compound having the formula R(Me), where R represents a hydrocarbyl group containing from one to about 20 carbon atoms, and Me is a Group IA alkali metal atom, with (ii) a particle as defined above, in the presence of (iii) a polar coordinator, to form the reaction product having the formula P(Me) n , where P represents the particle having covalently bonded alkali metal atoms and n is the same as previously described
  • the molar ratio of the polar coordinator to the alkali metal compound is about 0.03:1 to about 4:1, preferably about 0.05:1 to about 1:1, and more preferably about 0.06:1 to about 0.5:1.
  • FIG. 1 is a schematic illustration of an invention initiator comprising a particle metalated with three alkali metal atoms.
  • FIG. 2 is a schematic illustration of the initiator of FIG. 1 metalated with a multiplicity of surface-bound alkali metal atoms.
  • FIG. 3 is a schematic illustration of an invention initiator comprising the particle where the inner matrix of the particle is multiply metalated.
  • FIG. 4 is a schematic illustration of an invention initiator comprising the particle where both the surface and the inner matrix of the particle are multiply metalated.
  • FIG. 5 is a schematic illustration of the macro-branched diene polymer formed with the invention initiator.
  • the invention provides a novel solid supported anionic polymerization initiator for anionic polymerization of conjugated diolefin monomers having from about 4 to about 12 carbon atoms, and copolymerization of the conjugated diolefin monomers together with monovinyl aromatic monomers having from about 8 to about 20 carbon atoms, as described below, to form a macro-branched diene polymer.
  • the initiator has the formula
  • P is a metalatable particle having a diameter of about 1 micron to about 1000 microns comprising a thermoplastic polymer or a cured elastomer
  • Me is a Group IA alkali metal covalently bonded to the particle
  • n is an integer equal to or greater than 3. More preferably, n represents a multiplicity of alkali metal atoms (Me), 10 x (e.g., 10 10 ), and the particle comprises a multiplicity of covalently bonded alkali metal atoms.
  • the metal atoms may be any Group IA alkali metal including lithium, sodium, potassium, rubidium, cesium and francium. Although rubidium, cesium and francium are usable in the invention initiator, their use is less preferred because they are comparatively expensive. Therefore, the metal atoms are preferably lithium, sodium or potassium atoms, and more preferably are a mixture of lithium atoms and sodium atoms and/or potassium atoms. Most preferably, all of the alkali metal atoms are lithium.
  • the alkali metal atoms on a single particle may all be the same or may be different from each other, depending on the alkali metal compound(s) used for the preparation of the initiator, as described below.
  • a single alkali metal compound such as an alkyl lithium, an alkyl sodium, an alkyl potassium or another Group IA alkyl metal compound
  • the use of a mixture of an alkyl lithium compound together with an alkyl sodium compound and/or an alkyl potassium compound and/or another Group IA alkyl metal compound as a co-agent for metalation produces particles metalated with lithium, as well as sodium and/or potassium and/or the other metal.
  • an alkyl lithium compound alone is used in the preparation of the initiators, resulting in a particle metalated only with lithium.
  • the particle 2 has a multiplicity of alkali metal atoms 3 bonded to a multiplicity of carbon atoms on the particle.
  • the particle 2 comprises an outer surface 4 and an inner matrix 5.
  • the alkali metal atoms 3 may be covalently bonded to the outer surface 4 (FIG. 2), or to the inner matrix 5 (FIG. 3), or to both the outer surface 4 and the inner matrix 5 (FIG. 4).
  • the particle comprises a metalatable thermoplastic polymer.
  • Suitable metalatable thermoplastic polymers for use in the invention include, but are not limited to, polyethylene, polypropylene, polystyrenes, substituted polystyrenes, and the like. Other such metalatable thermoplastic polymers are well known to those skilled in the art.
  • the thermoplastic polymer preferably has a T g of 800° C. to about 300° C.
  • the processing temperatures are higher than the T g of the thermoplastic polymer particle and allow the breakup of the thermoplastic particle into smaller particles that could, in the limit, contain only one polymer/elastomer chain attached to the particle, thus allowing for better processibility of the polymers.
  • the particle comprises a metalatable cured elastomer.
  • the cured elastomer may be any metalatable cured elastomer known to those skilled in the art, including compounded cured rubber, such as scrap tire rubber.
  • Exemplary cured elastomers suitable for use in the invention are styrene butadiene rubber, natural rubber, polybutadiene, polyisoprene, and the like.
  • Other such metalatable cured elastomers are well known to those skilled in the art.
  • the compounded cured rubber particle is preferably extracted with acetone for at least 16 hours to substantially remove at least the curing agents, prior to use in preparation of the initiator.
  • the macro-branched polymers that include the cured elastomeric particles described above are compounded or milled, the points of attachment of the polymers to the particles are shear-degraded, thus allowing for better processibility of the polymers.
  • the particles having a diameter of about 1 to about 1000 microns, may be conveniently sized by passing them through a mesh of fixed pore size, as is well known in the art.
  • 20-mesh particles are about 841 microns or less in diameter
  • 200-mesh particles are about 74 microns or less
  • 400-mesh particles are about 37 microns or less.
  • the number of metalation sites on the particles depends on the size of the particles, the concentrations of the alkali metal compound and the polar coordinator employed in the metalation reaction, the process times and temperatures, and the like.
  • the method comprises the step of reacting (i) an alkali metal compound having the formula R(Me), where R represents a hydrocarbyl group containing from one to about 20 carbon atoms and Me is a Group IA alkali metal, with (ii) a particle as described above, in the presence of (iii) a polar coordinator.
  • the polar coordinator is an activator of the Group IA alkali metal atom and, as known to one skilled in the art, is required for the formation of the carbon atom-metal atom covalent bond during metalation of the particle.
  • the initiators according to the present invention can be prepared, under anhydrous and anaerobic conditions, by forming a suspension of the thermoplastic polymer or cured elastomer particles described above in an anhydrous hydrocarbon solvent, such as cyclohexane, hexane, benzene, toluene, pentane, heptane, and the like, in a dry nitrogen atmosphere. To this suspension is then added a polar coordinator, followed by the addition of an alkali metal compound, described below, in the same or a similar solvent.
  • an anhydrous hydrocarbon solvent such as cyclohexane, hexane, benzene, toluene, pentane, heptane, and the like
  • the molar ratio of the polar coordinator to the alkali metal compound ranges from about 0.03:1 to about 4:1, preferably about 0.05:1 to about 1:1, and more preferably about 0.06:1 to about 0.5:1.
  • the optimum amount of particles present in the reaction mixture varies with the selected ratio of polar coordinator to alkali metal compound, the type of particle employed, the particle diameter, and the degree of metalation desired.
  • One skilled in the art will be able to select the proper amount of particles by examining the exemplary data reported herein in Table 1.
  • the various reaction temperatures and times which may be employed to prepare the initiators are known to one skilled in the art of anionic polymerization initiator preparation.
  • the alkali metal compound employed in the preparation of the solid supported anionic initiators has the formula R(Me), where Me is a metal of Group IA of the Periodic Table of the Elements preferably selected from lithium, sodium and potassium, and more preferably is lithium, and R is a hydrocarbyl group having from one to about 20 carbon atoms.
  • R is a hydrocarbyl group having from one to about 20 carbon atoms.
  • lithium alkali metal compounds are most preferred in the method, sodium and/or potassium and/or other Group IA alkali metal compounds may also be separately employed.
  • these other compounds are used in a mixture with a lithium compound and the sodium and/or potassium and/or other Group IA compound acts as a co-agent with the lithium compound for metalation.
  • the resulting particles may be metalated with one or more types of alkali metal atoms derived from the alkali metal compound(s).
  • R groups include aliphatic and cyclo-aliphatic groups such as alkyls, cycloalkyls, alkenyls, alkynyls, aryls and aralkyls.
  • R groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-hexyl, n-octyl, n-decyl, cyclopentyl-methyl, cyclohexyl-ethyl, cyclopentyl-ethyl, methyl-cyclopentylethyl, cyclopentyl, cyclohexyl, 2,2,1-bicycloheptyl, methylcyclopentyl, dimethylcyclopentyl, ethylcyclopentyl, methylcyclo
  • Each metalated particle thus prepared is a solid supported initiator that is stable for at least a month or more and is useful for anionic polymerization of anionically-polymerizable monomers to yield a macro-branched polymeric product. Because of the polymeric nature of the particles, each particle readily absorbs the hydrocarbon solvent and is thus is best described as a highly swollen particle. For example, each gram of a 200-mesh scrap rubber particle may contain two to five grams of a solvent in its inner matrix.
  • the swollen particle is metalated with at least three or, preferably, a multiplicity of metal atoms, depending on the selected reaction conditions.
  • Metalation of the particle occurs in the presence of a polar coordinator associated with the polymer carbon-metal bond.
  • a polar coordinator associated with the polymer carbon-metal bond.
  • Such metalation reactions employing a polar coordinator are known to those skilled in the art.
  • the polar coordinator remains associated with the carbon-metal bond of the initiator throughout the anionic polymerization process.
  • the presence of the polar coordinator associated with the initiator results in a modification of diene polymerization that gives a reduced level of 1,4 incorporation of monomers and a concomitant increase in the T g of the polymer produced (i.e., the higher the concentration of the polar coordinator in the polymerization reaction mixture, the higher is the glass transition temperature (T g ) of the resulting diene polymer).
  • the conventional procedure for preparing a standard (non-invention) metalated polymer from an alkali metal compound and a polar coordinator employs a molar ratio of the polar coordinator to the alkali metal of about 2:1.
  • the polymerization result would be a high T g graft copolymer product (e.g., a very high vinyl polybutadiene grafted onto a low vinyl 1,4-polybutadiene). It is an object of the present invention to produce polymers having a low T g , preferably less than -20° C., more preferably less than -30° C., and most preferably less than -35° C., for use in rubber products, such as tires. Therefore, it is desirable to prepare the present initiators in the presence of a lower than standard molar ratio of polar coordinator to alkali metal compound.
  • Compounds useful as polar coordinators are organic and include, but are not limited to, tetrahydrofuran, linear and cyclic oligomeric oxolanyl alkanes such as 2-2'-di(tetrahydrofuryl) propane, dipiperidyl ethane, dimethyl ether, pentamethyl diethylenediamine, diazabicyclooctane, hexamethylphosphoramide, N-N'-dimethylpiperazine, diethyl ether, tributylamine and the like.
  • the linear and cyclic oligomeric oxolanyl alkane polar coordinators are described in U.S. Pat. No.
  • polar coordinators include those having an oxygen or nitrogen hetero-atom and a non-bonded pair of electrons.
  • Examples include dialkyl ethers of mono and oligo alkylene glycols; "crown" ethers; fully alkylated diamines such as tetramethylethylene diamine (TMEDA); and fully alkylated triamines.
  • the initiators prepared according to the method of the invention are employed with an anionically-polymerizable monomer to yield macro-branched diene polymers having the formula
  • polymer represents a polymer chain covalently bonded to the particle
  • the polymer component of the polymer chain is preferably selected from conjugated diolefin monomers having from about 4 to about 12 carbon atoms, and copolymers and terpolymers of the conjugated diolefin monomers together with monovinyl aromatic monomers having from about 8 to about 20 carbon atoms.
  • the monomers are selected from styrene, butadiene, isoprene, and mixtures of these.
  • vulcanizable elastomer compositions are prepared from the macro-branched diene polymers by compounding the polymers with about 5 to about 80 parts by weight of carbon black per 100 parts by weight of the polymer.
  • the vulcanizable elastomer composition comprises a selection from the group consisting of styrene butadiene rubber, polybutadiene rubber, polyisoprene rubber, isoprene butadiene rubber, terpolymer rubbers of styrene, butadiene and isoprene, and mixtures of these rubbers.
  • prior to quenching comprises the step of polymerizing at least one monomer selected from the group consisting of conjugated diolefin monomers having from about 4 to about 12 carbon atoms and monovinyl aromatic monomers having from about 8 to about 20 carbon atoms, in the presence of an anionic polymerization initiator having the formula P(Me) n , wherein P represents the particle metalated with n covalently bonded alkali metal atoms, as described above.
  • the initiator is used to polymerize unsaturated hydrocarbon monomers such as butadiene, isoprene and the like, and copolymers thereof with monovinyl aromatics such as styrene and its derivatives such as a-methyl styrene, p-methyl styrene and the like.
  • the macro-branched elastomeric products include diene homopolymers from monomer A and copolymers thereof with monovinyl aromatic monomers B.
  • Exemplary diene homopolymers are those prepared from conjugated diolefin monomers having from 4 to about 12 carbon atoms.
  • Exemplary vinyl aromatic copolymers are those prepared from monomers having from 8 to about 20 carbon atoms.
  • Preferred macro-branched elastomers include diene homopolymers, such as polybutadiene and polyisoprene, copolymers, such as styrene butadiene rubber and isoprene butadiene rubber, and terpolymers consisting of styrene, butadiene and isoprene.
  • Copolymers and terpolymers can comprise from about 99 to 10 percent by weight of diene units and from about 1 to about 90 percent by weight of monovinyl aromatic units, totaling 100 percent.
  • the polymers, copolymers and terpolymers of the present invention may have 1,2-microstructure contents ranging from about 10 to about 80 percent, with the preferred polymers, copolymers or terpolymers having 1,2-microstructure contents of from about 25 to 65 percent, based upon the diene content.
  • the elastomeric copolymers are preferably random copolymers which result from simultaneous copolymerization of the monomers A and B with randomizing agents, as is known in the art.
  • Block copolymers, poly (b-styrene-b-butadiene-b-styrene) are thermoplastic elastomers, sometimes referred to as S-B-S polymers.
  • FIG. 5 is a schematic representation of a macro-branched polymer 20 produced employing the invention initiators.
  • a polymer chain 12 can potentially be polymerized from each metalated site of the highly swollen particle 10. However in practice, where there are a large multiplicity of metalated sites, it is likely some of the sites may be unavailable because they may be concealed or partially concealed by adjacent growing polymer chains and the like. In this case, at least a majority of the metalated sites are available to produce polymer chains.
  • the metal atom 14 is carried on the living end of the polymer chain prior to quenching.
  • each particle may comprise from three to a multiplicity of polymer chains.
  • polymer chains may be produced at metalated sites in the inner matrix of the particle, since polymerizable monomers are dissolved in solvent that can enter the particle and are also soluble in both the particle and in the growing polymer chains.
  • the polymer chains may be any of the foregoing diene homopolymers, monovinyl aromatic homopolymers, dienelmonovinyl aromatic random copolymers, block copolymers, or mixtures of any of the foregoing.
  • about 0.5% to about 1% of the polymer product may comprise the original particle used in the initiator.
  • the concentration of the particle in the product can be changed by varying parameters such as the degree of metalation of the particles, e.g., by changing the initiator preparation ingredient concentrations, the particle sizes, and the like, or changing the concentration of monomers in the polymerization reactions, and the like.
  • Polymerization is usually conducted in a conventional hydrocarbon solvent for anionic polymerizations, such as cyclohexane, hexane, benzene, toluene, pentane, heptane, and the like.
  • a polar coordinator is optionally added to the polymerization ingredients, amounts range between about 0.1 to about 90 or more equivalents per equivalent of the alkali metal. The amount depends on the type of polar coordinator that is employed, the amount of vinyl desired, the level of styrene employed and the temperature of the polymerizations, as well as the selected initiator.
  • polymerization is begun by charging a blend of the monomer(s) and solvent to a suitable reaction vessel, followed by the addition of the initiator.
  • the initiator is typically in the form of a slurry (suspension) in a hydrocarbon solvent that can be syringed into the reaction vessel.
  • the degree of metalation of the initiator particle is determined by titration.
  • the polymerization reaction is carried out under anhydrous, anaerobic conditions. Often, it is conducted under a dry, inert gas atmosphere.
  • the polymerization can be carried out at any convenient temperature, such as about -30° C. to about 200° C.
  • the peak temperature is maintained at from about 49° C. to about 149° C., and more preferably from about 80° C. to about 120° C. Polymerization is allowed to continue under agitation for about 0.15 to 24 hours.
  • the resulting polymer is quenched by a terminating agent that may be a protic quenching agent such as water, steam or an alcohol such as isopropanol, or a functionalizing agent described below, to obtain a macro-branched diene polymer.
  • a terminating agent that may be a protic quenching agent such as water, steam or an alcohol such as isopropanol, or a functionalizing agent described below.
  • the terminating agent is added to the reaction vessel, and the vessel is agitated for about 0.1 to about 4.0 hours. Quenching is usually conducted by stirring the polymer and quenching agent for about 0.25 hours to about 1.0 hour at temperatures of from about 30° C. to about 120° C. to ensure a complete reaction.
  • solvent is removed from the polymer by conventional techniques. These include steam or alcohol coagulation, thermal desolventization, or any other suitable method. Additionally, solvent may be removed by drum drying, extruder drying, vacuum drying or the like. Desolventization by drum-drying, coagulation in alcohol, steam or hot water desolventization, extruder drying, vacuum drying, spray drying, and combinations thereof are preferred.
  • An antioxidant such as butylated hydroxy toluene (BHT) and/or an antiozonant compound is usually added to the polymer or polymer cement at or before this stage.
  • Functionalizing agents may be employed as terminating agents. These agents are compounds that provide a functional group that remains on the end of the polymer chain. Any compounds providing terminal functionality (e.g., "endcapping") that are reactive with the polymer bound metal atom moiety can be selected to provide a desired functional group. However, it is preferable that the functionalizing agents are not also coupling agents (i.e., the functionalizing agents should not couple together the chain ends) so that the branched structure of the polymer is maintained. Functionalizing agents are particularly preferred when elastomers are polymerized by the process of the invention because the functional group promotes uniform and homogeneous mixing with fillers, such as silica and carbon black.
  • compounding of vulcanizable macro-branched elastomers, prepared by the process of the invention results in rubber products exhibiting improved physical properties, such as reduced hysteresis, which means a rubber product having increased rebound, decreased rolling resistance in tires, and lessened heat build-up when subjected to mechanical stress.
  • improved physical properties such as reduced hysteresis
  • examples of such compounds are alcohols, substituted aldimines, substituted ketimines, Michler's ketone, 1,3-dimethyl-2-imidazolidinone, 1-alkyl substituted pyrrolidinones, 1-aryl substituted pyrrolidinones, tributyl tin chloride, and mixtures of these.
  • reactive compounds include the terminators described in U.S. Pat. Nos.
  • the preferred final polymerization product the macro-branched diene polymer, resembles fish "caviar".
  • This product which contains the initiator particle, may then be compounded or milled to disperse the thermoplastic polymer particle or shear-degrade the cured elastomer particle in the center of the polymer, as described above, and reduce the polymer to a base molecular weight.
  • each of the polymer chains of the macro-branched polymer have a molecular weight of about 20,000 to about 500,000, preferably about 100,000 to about 200,000, thus producing a macro-branched polymer having molecular weights that are several orders of magnitude higher than known linear polymers as measured by conventional gel permeation chromatographic (GPC) techniques.
  • the polydispersity (the ratio of the molecular weight to the number molecular weight) of the polymers can be controlled over a wide range, from 1 to about 20, preferably 1 to about 5, and more preferably 1 to about 2.
  • the highly branched polymers produced according to the invention exhibit desirable properties in addition to their extremely high molecular weight.
  • the polymers exhibit excellent oil absorption properties and are easily compounded. They are also readily mixed with other polymers, such as styrene butadiene rubber, natural rubber, polybutadiene, and the like, to form a polymer blend.
  • the invention polymers also do not "cold flow” (i.e. a polymer "ball” retains its integrity as a ball over time, in contrast to a polymer that does exhibit "cold flow” and would "puddle”).
  • the macro-branched polymers synthesized by the process of the invention may also be compounded to form vulcanizable elastomeric compounds and articles that exhibit excellent resistance to wear and tear and reduced hysteresis properties.
  • Articles such as tires, shock absorbers, mounts, power belts and the like, will show an increase in rebound, a decrease in rolling resistance and have less heat build-up when mechanical stresses are applied, resulting in improved fuel economy.
  • Decreased rolling resistance is, of course, a useful property for pneumatic tires, both radial as well as bias ply types and thus, the vulcanizable elastomeric compositions of the present invention can be utilized to form treadstocks for such tires.
  • the composition can also be used to form other elastomeric tire components such as subtreads, black sidewalls, body ply skims, bead fillers and the like.
  • the polymers of the present invention can be utilized as 100 parts of the rubber in the treadstock compound, or they can be blended with any conventionally employed treadstock rubber which includes natural rubber, synthetic rubber and blends thereof.
  • the amounts can vary widely with a lower limit comprising about 10 to 20 percent by weight of the total rubber. The minimum amount will depend primarily upon the degree of hysteresis reduction desired.
  • the compounds can contain 10 to 100% by weight of the inventive polymer, with the balance, if any, being a conventional rubber.
  • the polymers can be compounded with all forms of carbon black in amounts ranging from about 5 to 80 parts by weight, per 100 parts of rubber (phr), with about 35 to 60 phr being preferred.
  • the carbon blacks may include any of the commonly available, commercially-produced carbon blacks. Examples of preferred carbon black compounds are described in U.S. Pat. No. 5,521,309, the subject matter of which, relating to carbon black compounds, is incorporated by reference herein. Silica can be used in place of all or part of the carbon black.
  • the reinforced rubber compounds can be cured in a conventional manner with known vulcanizing agents at about 0.1 to 10 phr.
  • suitable vulcanizing agents one can refer to Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd ed., Wiley lnterscience, N.Y. 1982, Vol. 20, pp. 365-468, particularly "Vulcanization Agents and Auxiliary Materials", pp. 390-402. Vulcanizing agents can be used alone or in combination.
  • Vulcanizable elastomeric compositions of the invention can be prepared by compounding or mixing the macro-branched polymers herein, with carbon black and other conventional rubber additives including, for example, fillers, such as silica, plasticizers, antioxidants, curing agents and the like, using standard rubber mixing equipment and procedures.
  • fillers such as silica, plasticizers, antioxidants, curing agents and the like
  • Such elastomeric compositions when vulcanized using conventional rubber vulcanization conditions, have reduced hysteresis properties and are particularly adapted for use as tread rubbers for tires having reduced rolling resistance.
  • acetone-extracted ground cured rubber particles i.e., substantially curative free particles
  • styrene butadiene rubber particles or natural rubber particles were reacted with a lithium hydrocarbyl compound in the presence of a polar coordinator to form multi-lithiated particles.
  • a polar coordinator to form multi-lithiated particles.
  • These initiators were then used to polymerize a solution of butadiene monomers.
  • the described particles, alkyl metal compound, polar coordinator, and solvents are intended to be only examples of those that may be used in the process of the invention, and their particular use is not intended to be limiting, as other particles, alkali metal compounds, polar coordinators and solvents may be utilized by those skilled in the art.
  • This example describes the preparation of a solid supported initiator employing 200 mesh ground scrap tire rubber (Rouse Rubber Industries) as the particles.
  • 200 mesh ground scrap tire rubber Rubber Industries
  • the particles Prior to use in preparing the initiator, the particles were extracted with acetone for at least 16 hours to remove substantially all curing agents.
  • the initiator was prepared in a 32-ounce beverage bottle that was dried by baking for at least 16 hours at 115° C. and then capped with a crown, two-hole cap and rubber liner. The bottle was cooled while purging with dry nitrogen and labeled as initiator #4. To the bottle was added 4.5 grams of the ground scrap rubber particles. The bottle was then capped and 50 grams of hexane was added, followed by purging with nitrogen.
  • the solid supported initiator in suspension was then stored under pressure in a cool environment (refrigerator) to prevent decomposition of the initiator.
  • This example describes the preparation of an initiator using a thermoplastic polymer as the particle.
  • the polymer employed is a copolymer of modified styrenes having a molecular weight of 2,900 and T g of 100° C., with the brand name ENDEX® 155 (Hercules Inc., Wilmington, Del.).
  • the initiator was prepared in a 32-ounce beverage bottle that was dried by baking for at least 16 hours at 115° C. and then capped with a crown, two-hole cap and rubber liner. The bottle was cooled while purging with dry nitrogen. To the bottle was added 5 grams of ENDEX®. Fifteen to 20 dry marbles were added to the bottle.
  • the bottle was then capped and 35 ml of hexane was added, followed by purging with nitrogen. Then 1.2 ml of 6.62 M TMEDA was added, followed by 15 ml of a 1.6 M solution of BuLi in hexane.
  • the bottle was heated in a 50° C. rotating bottle bath for 24 hours. The bottle was then removed from the bottle bath, allowed to cool to room temperature, and excess liquid was removed. The bottle was vigorously shaken on a mechanical shaker to smash large particles into small ones. The particles were then re-suspended in 50 grams of hexane.
  • the solid supported initiator in suspension was then stored under pressure in a cool environment (refrigerator) to prevent decomposition of the initiator.
  • the polymer was prepared in a 32-ounce beverage bottle that was dried by baking for at least 16 hours at 115° C. and then cooled while purging with dry nitrogen. The bottle was then capped with a crown, two-hole cap and rubber liner, pressure checked and again nitrogen purged. The bottle was labeled as polymer #P-18 and then placed in a bottle guard. To the bottle was added 50 grams of hexane, followed by 150 grams of 33% by weight butadiene in hexane. Finally, 5 ml of invention initiator #4, prepared as in Example 1, was added. The bottle was inserted into a 50° C. rotating bottle bath for 24 hours.
  • the bottle was then removed from the bottle bath and 2.0 ml of isopropanol (neat) was added to terminate the polymer.
  • the bottle was then allowed to cool to room temperature.
  • the contents in the bottle appeared more as a "solid” than a "liquid”, and appeared very similar to a fish "caviar”.
  • the hexanes in the bottle were swollen in the polymer that was produced.
  • the bottle was vented, then cut open and the polymer was isolated by removing the solvent on a drum dryer.
  • the resulting processed product sheeted on the rolls of the drum dryer and was easily gathered.
  • Table 2 illustrate properties of polymers similarly prepared employing the initiators described in Table 1.
  • Some of the polymers are copolymers of butadiene and styrene, prepared by standard polymerization procedures known to those skilled in the art.
  • the preferred polymers were macro-branched, having high number molecular weights (Mn) ranging from 72,000 to 594,000, Mooney viscosities at 100° C. ranging from 35 to 135, with a low polydispersity, a low 1,2-microstructure, and a T g between -35° C. and -75° C., preferably about -35° C. to -55° C.
  • Mn number molecular weight
  • Mooney viscosities at 100° C. ranging from 35 to 135
  • T g between -35° C. and -75° C., preferably about -35° C. to -55° C.
  • polymers containing styrene showed a higher T g than those without styrene.
  • all of the prepared polymers listed in Table 2 had an acceptable T g of less than -20° C.
  • Preferred polymers also had a high percentage of conversion of monomers and a low percentage of "soluble" polymer (i.e., free homopolymer).
  • Exemplary preferred polymers shown in Table 2 are #P-10 made with initiator #3; #P-18, #P-19, #-P-20 and #P-25 all made with initiator #4; #P-35 made with initiator #7; #P-37 made with initiator #8; #P-53 made with initiator #9; #P-54 and #P-55 made with initiator #10, and #P-62 and #P-63 made with initiator #11.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerization Catalysts (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
US09/042,096 1998-03-13 1998-03-13 Anionic polymerization initiators for preparing macro-branched diene rubbers Expired - Lifetime US6136914A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US09/042,096 US6136914A (en) 1998-03-13 1998-03-13 Anionic polymerization initiators for preparing macro-branched diene rubbers
EP99103963A EP0942004A3 (fr) 1998-03-13 1999-03-09 Initiateurs de polymérisation anionique pour la préparation de caoutchoucs de diènes ramifiés
CA002265238A CA2265238A1 (fr) 1998-03-13 1999-03-11 Initiateurs de polymerisation anionique pour la preparation de caoutchoucs dieniques ramifies
JP11064984A JPH11315108A (ja) 1998-03-13 1999-03-11 マクロ分岐を有するジエン系ゴムを製造するためのアニオン重合開始剤
ARP990101094A AR018748A1 (es) 1998-03-13 1999-03-12 Iniciadores de polimerizacion anionicos de dienos; polimeros macroramificados formados por la polimerizacion anionica de dienos con dichos iniciadores ymetodo de polimerizacion de dienos utilizando dichos iniciadores.
BR9902331-8A BR9902331A (pt) 1998-03-13 1999-03-15 Iniciadores de polimerização aniÈnica para a preparação de borrachas diênicas macrorramificados.
US09/569,253 US6271314B1 (en) 1998-03-13 2000-05-11 Anionic polymerization initiators for preparing macro-branched diene rubbers
US09/852,507 US6384150B2 (en) 1998-03-13 2001-05-10 Anionic polymerization initiators for preparing macro-branched diene rubbers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US09/042,096 US6136914A (en) 1998-03-13 1998-03-13 Anionic polymerization initiators for preparing macro-branched diene rubbers

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US09/569,253 Division US6271314B1 (en) 1998-03-13 2000-05-11 Anionic polymerization initiators for preparing macro-branched diene rubbers

Publications (1)

Publication Number Publication Date
US6136914A true US6136914A (en) 2000-10-24

Family

ID=21920025

Family Applications (3)

Application Number Title Priority Date Filing Date
US09/042,096 Expired - Lifetime US6136914A (en) 1998-03-13 1998-03-13 Anionic polymerization initiators for preparing macro-branched diene rubbers
US09/569,253 Expired - Lifetime US6271314B1 (en) 1998-03-13 2000-05-11 Anionic polymerization initiators for preparing macro-branched diene rubbers
US09/852,507 Expired - Lifetime US6384150B2 (en) 1998-03-13 2001-05-10 Anionic polymerization initiators for preparing macro-branched diene rubbers

Family Applications After (2)

Application Number Title Priority Date Filing Date
US09/569,253 Expired - Lifetime US6271314B1 (en) 1998-03-13 2000-05-11 Anionic polymerization initiators for preparing macro-branched diene rubbers
US09/852,507 Expired - Lifetime US6384150B2 (en) 1998-03-13 2001-05-10 Anionic polymerization initiators for preparing macro-branched diene rubbers

Country Status (6)

Country Link
US (3) US6136914A (fr)
EP (1) EP0942004A3 (fr)
JP (1) JPH11315108A (fr)
AR (1) AR018748A1 (fr)
BR (1) BR9902331A (fr)
CA (1) CA2265238A1 (fr)

Cited By (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6255406B1 (en) * 1998-03-13 2001-07-03 Bridgestone Corporation Gas phase anionic polymerization of diene elastomers
US20030176573A1 (en) * 2000-08-23 2003-09-18 Michael Grun Metallized unsaturated polymer anions, stabilized by a coordinate bond and having a large portion of cis double bonds
US20060074197A1 (en) * 2002-08-30 2006-04-06 Hogan Terrence E Functionalized polymers and improved vulcanizates therefrom
US20090209708A1 (en) * 2008-02-20 2009-08-20 Hergenrother William L Gas-phase anionic polymerization
US20100013489A1 (en) * 1999-11-01 2010-01-21 Vonderhaar J David Electronic battery tester
WO2011109343A3 (fr) * 2010-03-03 2011-10-27 Midtronics, Inc. Dispositif de surveillance pour des batteries à bornes frontales
US8164343B2 (en) 2003-09-05 2012-04-24 Midtronics, Inc. Method and apparatus for measuring a parameter of a vehicle electrical system
US8198900B2 (en) 1996-07-29 2012-06-12 Midtronics, Inc. Automotive battery charging system tester
US8203345B2 (en) 2007-12-06 2012-06-19 Midtronics, Inc. Storage battery and battery tester
US8237448B2 (en) 2000-03-27 2012-08-07 Midtronics, Inc. Battery testers with secondary functionality
US8306690B2 (en) 2007-07-17 2012-11-06 Midtronics, Inc. Battery tester for electric vehicle
US8344685B2 (en) 2004-08-20 2013-01-01 Midtronics, Inc. System for automatically gathering battery information
US8436619B2 (en) 2004-08-20 2013-05-07 Midtronics, Inc. Integrated tag reader and environment sensor
US8442877B2 (en) 2004-08-20 2013-05-14 Midtronics, Inc. Simplification of inventory management
US8493022B2 (en) 1997-11-03 2013-07-23 Midtronics, Inc. Automotive vehicle electrical system diagnostic device
US8513949B2 (en) 2000-03-27 2013-08-20 Midtronics, Inc. Electronic battery tester or charger with databus connection
US8674654B2 (en) 1997-11-03 2014-03-18 Midtronics, Inc. In-vehicle battery monitor
US8674711B2 (en) 2003-09-05 2014-03-18 Midtronics, Inc. Method and apparatus for measuring a parameter of a vehicle electrical system
US8738309B2 (en) 2010-09-30 2014-05-27 Midtronics, Inc. Battery pack maintenance for electric vehicles
US8872516B2 (en) 2000-03-27 2014-10-28 Midtronics, Inc. Electronic battery tester mounted in a vehicle
US8872517B2 (en) 1996-07-29 2014-10-28 Midtronics, Inc. Electronic battery tester with battery age input
US8958998B2 (en) 1997-11-03 2015-02-17 Midtronics, Inc. Electronic battery tester with network communication
US9018958B2 (en) 2003-09-05 2015-04-28 Midtronics, Inc. Method and apparatus for measuring a parameter of a vehicle electrical system
US9201120B2 (en) 2010-08-12 2015-12-01 Midtronics, Inc. Electronic battery tester for testing storage battery
US9229062B2 (en) 2010-05-27 2016-01-05 Midtronics, Inc. Electronic storage battery diagnostic system
US9244100B2 (en) 2013-03-15 2016-01-26 Midtronics, Inc. Current clamp with jaw closure detection
US9255955B2 (en) 2003-09-05 2016-02-09 Midtronics, Inc. Method and apparatus for measuring a parameter of a vehicle electrical system
US9274157B2 (en) 2007-07-17 2016-03-01 Midtronics, Inc. Battery tester for electric vehicle
US9312575B2 (en) 2013-05-16 2016-04-12 Midtronics, Inc. Battery testing system and method
US9419311B2 (en) 2010-06-18 2016-08-16 Midtronics, Inc. Battery maintenance device with thermal buffer
US9496720B2 (en) 2004-08-20 2016-11-15 Midtronics, Inc. System for automatically gathering battery information
US9588185B2 (en) 2010-02-25 2017-03-07 Keith S. Champlin Method and apparatus for detecting cell deterioration in an electrochemical cell or battery
US9851411B2 (en) 2012-06-28 2017-12-26 Keith S. Champlin Suppressing HF cable oscillations during dynamic measurements of cells and batteries
US9923289B2 (en) 2014-01-16 2018-03-20 Midtronics, Inc. Battery clamp with endoskeleton design
US9966676B2 (en) 2015-09-28 2018-05-08 Midtronics, Inc. Kelvin connector adapter for storage battery
US10046649B2 (en) 2012-06-28 2018-08-14 Midtronics, Inc. Hybrid and electric vehicle battery pack maintenance device
US10222397B2 (en) 2014-09-26 2019-03-05 Midtronics, Inc. Cable connector for electronic battery tester
US10317468B2 (en) 2015-01-26 2019-06-11 Midtronics, Inc. Alternator tester
US10429449B2 (en) 2011-11-10 2019-10-01 Midtronics, Inc. Battery pack tester
US10473555B2 (en) 2014-07-14 2019-11-12 Midtronics, Inc. Automotive maintenance system
US10608353B2 (en) 2016-06-28 2020-03-31 Midtronics, Inc. Battery clamp
US10843574B2 (en) 2013-12-12 2020-11-24 Midtronics, Inc. Calibration and programming of in-vehicle battery sensors
US11054480B2 (en) 2016-10-25 2021-07-06 Midtronics, Inc. Electrical load for electronic battery tester and electronic battery tester including such electrical load
US11325479B2 (en) 2012-06-28 2022-05-10 Midtronics, Inc. Hybrid and electric vehicle battery maintenance device
US11474153B2 (en) 2019-11-12 2022-10-18 Midtronics, Inc. Battery pack maintenance system
US11486930B2 (en) 2020-01-23 2022-11-01 Midtronics, Inc. Electronic battery tester with battery clamp storage holsters
US11513160B2 (en) 2018-11-29 2022-11-29 Midtronics, Inc. Vehicle battery maintenance device
US11545839B2 (en) 2019-11-05 2023-01-03 Midtronics, Inc. System for charging a series of connected batteries
US11566972B2 (en) 2019-07-31 2023-01-31 Midtronics, Inc. Tire tread gauge using visual indicator
US11650259B2 (en) 2010-06-03 2023-05-16 Midtronics, Inc. Battery pack maintenance for electric vehicle
US11668779B2 (en) 2019-11-11 2023-06-06 Midtronics, Inc. Hybrid and electric vehicle battery pack maintenance device
US11740294B2 (en) 2010-06-03 2023-08-29 Midtronics, Inc. High use battery pack maintenance
US11973202B2 (en) 2019-12-31 2024-04-30 Midtronics, Inc. Intelligent module interface for battery maintenance device

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100347205C (zh) * 2001-04-11 2007-11-07 旭化成株式会社 氢化聚合物及其生产方法
JP4633115B2 (ja) * 2005-03-29 2011-02-16 旭化成ケミカルズ株式会社 変性ブタジエン系重合体組成物
US20090156763A1 (en) * 2005-08-30 2009-06-18 Roberta Sulcis Process for manufacturing a thermoplastic elastomeric material
JP4708210B2 (ja) * 2006-02-21 2011-06-22 株式会社ブリヂストン ゴム組成物及びそれを使用した空気入りタイヤ
JP2009545654A (ja) * 2006-08-01 2009-12-24 アルベマール・コーポレーシヨン スチレン重合体中におけるリチウムの低減
RU2485146C2 (ru) * 2007-12-31 2013-06-20 Бриджстоун Корпорейшн Способ получения полимерной композиции и полимерная композиция
DE102009026185A1 (de) * 2009-07-16 2011-02-10 Elantas Gmbh Reaktiv-Systeme
WO2011087841A1 (fr) 2009-12-22 2011-07-21 Bridgestone Corporation Composition améliorée de modification de la teneur en vinyle et procédés d'utilisation d'une telle composition
CN103626926B (zh) 2012-08-21 2016-03-30 中国石油化工股份有限公司 一种聚丁二烯接枝异戊橡胶及其制备方法和硫化胶及混炼胶
JP6557812B2 (ja) * 2014-05-08 2019-08-14 熊本県 複合粒子およびその製造方法

Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3703566A (en) * 1969-08-07 1972-11-21 Intern Synthetic Rubber Co The Graft copolymerisation process
GB1451280A (en) * 1973-06-20 1976-09-29 Mobil Oil Corp Organic reinforcing fillers for rubber
US4129701A (en) * 1974-12-16 1978-12-12 Standard Oil Company (Indiana) Horizontal reactor for the vapor phase polymerization of monomers
US4429091A (en) * 1983-03-09 1984-01-31 The Firestone Tire & Rubber Company Oligomeric oxolanyl alkanes as modifiers for polymerization of dienes using lithium-based initiators
US4476240A (en) * 1982-07-01 1984-10-09 The Firestone Tire & Rubber Company Catalyst system containing an anionic initiator based on lithium and phosphine oxide modifier
US4520123A (en) * 1984-07-02 1985-05-28 The Firestone Tire & Rubber Company Catalyst system and process for polymerizing conjugated dienes
US4707521A (en) * 1986-03-12 1987-11-17 The Dow Chemical Company Process for metallating crystalline ethylene-nonconjugated diene polymers and graft polymers prepared therefrom
US4761456A (en) * 1985-06-17 1988-08-02 The Dow Chemical Company Process for metallating nonconjugated diene-containing ethylene polymers and graft polymers prepared therefrom
US4861742A (en) * 1987-09-01 1989-08-29 Basf Aktiengesellschaft Bifunctional alkali metal compounds, preparation and use thereof as polymerization initiators
EP0475603A1 (fr) * 1990-08-31 1992-03-18 BP Chemicals Limited Procédé de polymérisation en phase gazeuse
US5208303A (en) * 1989-08-08 1993-05-04 Bp Chemicals Limited Process for preparing a vanadium-based catalyst suitable for olefin polymerization
US5221716A (en) * 1990-03-26 1993-06-22 The Goodyear Tire & Rubber Company Comb polymers having a halobutyl rubber backbone
US5238893A (en) * 1991-12-30 1993-08-24 Bridgestone Corporation Method of preparing an anionic polymerization initiator
US5252688A (en) * 1990-01-03 1993-10-12 Bp Chemicals Limited Process for preparing a Ziegler-Natta type catalyst
US5264506A (en) * 1992-12-30 1993-11-23 Union Carbide Chemicals & Plastics Technology Corporation Process for producing sticky polymers
US5268439A (en) * 1991-01-02 1993-12-07 Bridgestone/Firestone, Inc. Tin containing elastomers and products having reduced hysteresis properties
US5268413A (en) * 1990-04-09 1993-12-07 Bridgestone/Firestone, Inc. Elastomers and products having reduced hysteresis
US5317036A (en) * 1992-10-16 1994-05-31 Union Carbide Chemicals & Plastics Technology Corporation Gas phase polymerization reactions utilizing soluble unsupported catalysts
US5329005A (en) * 1992-10-02 1994-07-12 Bridgestone Corporation Soluble anionic polymerization initiators and preparation thereof
US5332810A (en) * 1992-10-02 1994-07-26 Bridgestone Corporation Solubilized anionic polymerization initiator and preparation thereof
US5354822A (en) * 1990-04-09 1994-10-11 Bridgestone/Firestone, Inc. Methods for preparing functionalized polymer and elastomeric compounds having reduced hysteresis
CA2133526A1 (fr) * 1993-10-06 1995-04-07 Gerd Sylvester Catalyseur, sa production et son utilisation pour la polymerisation en phase gazeuse de dienes conjugues
WO1996004321A1 (fr) * 1994-08-02 1996-02-15 Union Carbide Chemicals & Plastics Technology Corporation Procede de polymerisation en phase gazeuse
WO1997008211A1 (fr) * 1995-08-31 1997-03-06 The Goodyear Tire & Rubber Company Synthese en phase vapeur de polymeres caoutchouteux
US5665826A (en) * 1995-07-21 1997-09-09 The Goodyear Tire & Rubber Company Pneumatic tire

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976628A (en) * 1968-12-18 1976-08-24 The Firestone Tire & Rubber Company Process for polylithiating unsaturated polymers
US4134938A (en) * 1976-08-12 1979-01-16 Exxon Research & Engineering Co. Process for polymer lithiation in graft polymerization
US4297451A (en) * 1979-07-10 1981-10-27 Phillips Petroleum Company Dienyllithium initiated polymers
JPH0755964B2 (ja) * 1985-12-28 1995-06-14 旭化成工業株式会社 改良されたゴム状重合体の製造方法
IT1234389B (it) * 1989-04-06 1992-05-18 Himont Inc Polimeri funzionalizzati da copolimeri cristallini metallati delle olefine con dieni e relativo processo di preparazione.
FR2717797B1 (fr) * 1994-03-24 1996-04-26 Atochem Elf Sa Dérivés du 1, 5-diéthényl-naphtalène, leur procédé de fabrication, et leur utilisation comme précurseurs d'amorceurs difonctionnels en polymérisation anionique.
FR2723953B1 (fr) * 1994-08-25 1996-09-20 Atochem Elf Sa Amorceur multifonctionnel pour l'obtention de polymeres en etoile par voie anionique, son procede de fabrication, et polymeres en etoile correspondants, leur procede de fabrication et leurs applications
US6071847A (en) 1998-03-13 2000-06-06 Bridgestone Corporation Gas phase anionic polymerization of diene elastomers

Patent Citations (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3703566A (en) * 1969-08-07 1972-11-21 Intern Synthetic Rubber Co The Graft copolymerisation process
GB1451280A (en) * 1973-06-20 1976-09-29 Mobil Oil Corp Organic reinforcing fillers for rubber
US4129701A (en) * 1974-12-16 1978-12-12 Standard Oil Company (Indiana) Horizontal reactor for the vapor phase polymerization of monomers
US4476240A (en) * 1982-07-01 1984-10-09 The Firestone Tire & Rubber Company Catalyst system containing an anionic initiator based on lithium and phosphine oxide modifier
US4429091A (en) * 1983-03-09 1984-01-31 The Firestone Tire & Rubber Company Oligomeric oxolanyl alkanes as modifiers for polymerization of dienes using lithium-based initiators
US4520123A (en) * 1984-07-02 1985-05-28 The Firestone Tire & Rubber Company Catalyst system and process for polymerizing conjugated dienes
US4761456A (en) * 1985-06-17 1988-08-02 The Dow Chemical Company Process for metallating nonconjugated diene-containing ethylene polymers and graft polymers prepared therefrom
US4707521A (en) * 1986-03-12 1987-11-17 The Dow Chemical Company Process for metallating crystalline ethylene-nonconjugated diene polymers and graft polymers prepared therefrom
US4861742A (en) * 1987-09-01 1989-08-29 Basf Aktiengesellschaft Bifunctional alkali metal compounds, preparation and use thereof as polymerization initiators
US5208303A (en) * 1989-08-08 1993-05-04 Bp Chemicals Limited Process for preparing a vanadium-based catalyst suitable for olefin polymerization
US5252688A (en) * 1990-01-03 1993-10-12 Bp Chemicals Limited Process for preparing a Ziegler-Natta type catalyst
US5221716A (en) * 1990-03-26 1993-06-22 The Goodyear Tire & Rubber Company Comb polymers having a halobutyl rubber backbone
US5268413A (en) * 1990-04-09 1993-12-07 Bridgestone/Firestone, Inc. Elastomers and products having reduced hysteresis
US5354822A (en) * 1990-04-09 1994-10-11 Bridgestone/Firestone, Inc. Methods for preparing functionalized polymer and elastomeric compounds having reduced hysteresis
EP0475603A1 (fr) * 1990-08-31 1992-03-18 BP Chemicals Limited Procédé de polymérisation en phase gazeuse
US5268439A (en) * 1991-01-02 1993-12-07 Bridgestone/Firestone, Inc. Tin containing elastomers and products having reduced hysteresis properties
US5238893A (en) * 1991-12-30 1993-08-24 Bridgestone Corporation Method of preparing an anionic polymerization initiator
US5329005A (en) * 1992-10-02 1994-07-12 Bridgestone Corporation Soluble anionic polymerization initiators and preparation thereof
US5332810A (en) * 1992-10-02 1994-07-26 Bridgestone Corporation Solubilized anionic polymerization initiator and preparation thereof
US5317036A (en) * 1992-10-16 1994-05-31 Union Carbide Chemicals & Plastics Technology Corporation Gas phase polymerization reactions utilizing soluble unsupported catalysts
US5264506A (en) * 1992-12-30 1993-11-23 Union Carbide Chemicals & Plastics Technology Corporation Process for producing sticky polymers
CA2133526A1 (fr) * 1993-10-06 1995-04-07 Gerd Sylvester Catalyseur, sa production et son utilisation pour la polymerisation en phase gazeuse de dienes conjugues
WO1996004321A1 (fr) * 1994-08-02 1996-02-15 Union Carbide Chemicals & Plastics Technology Corporation Procede de polymerisation en phase gazeuse
US5665826A (en) * 1995-07-21 1997-09-09 The Goodyear Tire & Rubber Company Pneumatic tire
WO1997008211A1 (fr) * 1995-08-31 1997-03-06 The Goodyear Tire & Rubber Company Synthese en phase vapeur de polymeres caoutchouteux
US5652304A (en) * 1995-08-31 1997-07-29 The Goodyear Tire & Rubber Company Vapor phase synthesis of rubbery polymers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
U.S. application No. 09/041,719, Cole et al. *

Cited By (65)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8198900B2 (en) 1996-07-29 2012-06-12 Midtronics, Inc. Automotive battery charging system tester
US8872517B2 (en) 1996-07-29 2014-10-28 Midtronics, Inc. Electronic battery tester with battery age input
US8958998B2 (en) 1997-11-03 2015-02-17 Midtronics, Inc. Electronic battery tester with network communication
US8674654B2 (en) 1997-11-03 2014-03-18 Midtronics, Inc. In-vehicle battery monitor
US8493022B2 (en) 1997-11-03 2013-07-23 Midtronics, Inc. Automotive vehicle electrical system diagnostic device
US6255406B1 (en) * 1998-03-13 2001-07-03 Bridgestone Corporation Gas phase anionic polymerization of diene elastomers
US20100013489A1 (en) * 1999-11-01 2010-01-21 Vonderhaar J David Electronic battery tester
US8754653B2 (en) 1999-11-01 2014-06-17 Midtronics, Inc. Electronic battery tester
US9052366B2 (en) 2000-03-27 2015-06-09 Midtronics, Inc. Battery testers with secondary functionality
US8237448B2 (en) 2000-03-27 2012-08-07 Midtronics, Inc. Battery testers with secondary functionality
US8872516B2 (en) 2000-03-27 2014-10-28 Midtronics, Inc. Electronic battery tester mounted in a vehicle
US8513949B2 (en) 2000-03-27 2013-08-20 Midtronics, Inc. Electronic battery tester or charger with databus connection
US20030176573A1 (en) * 2000-08-23 2003-09-18 Michael Grun Metallized unsaturated polymer anions, stabilized by a coordinate bond and having a large portion of cis double bonds
US8207275B2 (en) 2002-08-30 2012-06-26 Bridgestone Corporation Functionalized polymers and improved vulcanizates therefrom
US20060074197A1 (en) * 2002-08-30 2006-04-06 Hogan Terrence E Functionalized polymers and improved vulcanizates therefrom
US7723440B2 (en) 2002-08-30 2010-05-25 Bridgestone Corporation Functionalized polymers and improved vulcanizates therefrom
US20100298465A1 (en) * 2002-08-30 2010-11-25 Hogan Terrence E Functionalized polymers and improved vulcanizates therefrom
US8674711B2 (en) 2003-09-05 2014-03-18 Midtronics, Inc. Method and apparatus for measuring a parameter of a vehicle electrical system
US9255955B2 (en) 2003-09-05 2016-02-09 Midtronics, Inc. Method and apparatus for measuring a parameter of a vehicle electrical system
US8164343B2 (en) 2003-09-05 2012-04-24 Midtronics, Inc. Method and apparatus for measuring a parameter of a vehicle electrical system
US9018958B2 (en) 2003-09-05 2015-04-28 Midtronics, Inc. Method and apparatus for measuring a parameter of a vehicle electrical system
US9496720B2 (en) 2004-08-20 2016-11-15 Midtronics, Inc. System for automatically gathering battery information
US8344685B2 (en) 2004-08-20 2013-01-01 Midtronics, Inc. System for automatically gathering battery information
US8442877B2 (en) 2004-08-20 2013-05-14 Midtronics, Inc. Simplification of inventory management
US8704483B2 (en) 2004-08-20 2014-04-22 Midtronics, Inc. System for automatically gathering battery information
US8436619B2 (en) 2004-08-20 2013-05-07 Midtronics, Inc. Integrated tag reader and environment sensor
US8963550B2 (en) 2004-08-20 2015-02-24 Midtronics, Inc. System for automatically gathering battery information
US9335362B2 (en) 2007-07-17 2016-05-10 Midtronics, Inc. Battery tester for electric vehicle
US9274157B2 (en) 2007-07-17 2016-03-01 Midtronics, Inc. Battery tester for electric vehicle
US8306690B2 (en) 2007-07-17 2012-11-06 Midtronics, Inc. Battery tester for electric vehicle
US8203345B2 (en) 2007-12-06 2012-06-19 Midtronics, Inc. Storage battery and battery tester
US8362150B2 (en) 2008-02-20 2013-01-29 Bridgestone Corporation Gas-phase anionic polymerization
US20090209708A1 (en) * 2008-02-20 2009-08-20 Hergenrother William L Gas-phase anionic polymerization
US9588185B2 (en) 2010-02-25 2017-03-07 Keith S. Champlin Method and apparatus for detecting cell deterioration in an electrochemical cell or battery
WO2011109343A3 (fr) * 2010-03-03 2011-10-27 Midtronics, Inc. Dispositif de surveillance pour des batteries à bornes frontales
US9425487B2 (en) 2010-03-03 2016-08-23 Midtronics, Inc. Monitor for front terminal batteries
US9229062B2 (en) 2010-05-27 2016-01-05 Midtronics, Inc. Electronic storage battery diagnostic system
US11650259B2 (en) 2010-06-03 2023-05-16 Midtronics, Inc. Battery pack maintenance for electric vehicle
US11740294B2 (en) 2010-06-03 2023-08-29 Midtronics, Inc. High use battery pack maintenance
US9419311B2 (en) 2010-06-18 2016-08-16 Midtronics, Inc. Battery maintenance device with thermal buffer
US9201120B2 (en) 2010-08-12 2015-12-01 Midtronics, Inc. Electronic battery tester for testing storage battery
US8738309B2 (en) 2010-09-30 2014-05-27 Midtronics, Inc. Battery pack maintenance for electric vehicles
US10429449B2 (en) 2011-11-10 2019-10-01 Midtronics, Inc. Battery pack tester
US11926224B2 (en) 2012-06-28 2024-03-12 Midtronics, Inc. Hybrid and electric vehicle battery pack maintenance device
US11548404B2 (en) 2012-06-28 2023-01-10 Midtronics, Inc. Hybrid and electric vehicle battery pack maintenance device
US10046649B2 (en) 2012-06-28 2018-08-14 Midtronics, Inc. Hybrid and electric vehicle battery pack maintenance device
US9851411B2 (en) 2012-06-28 2017-12-26 Keith S. Champlin Suppressing HF cable oscillations during dynamic measurements of cells and batteries
US11325479B2 (en) 2012-06-28 2022-05-10 Midtronics, Inc. Hybrid and electric vehicle battery maintenance device
US9244100B2 (en) 2013-03-15 2016-01-26 Midtronics, Inc. Current clamp with jaw closure detection
US9312575B2 (en) 2013-05-16 2016-04-12 Midtronics, Inc. Battery testing system and method
US10843574B2 (en) 2013-12-12 2020-11-24 Midtronics, Inc. Calibration and programming of in-vehicle battery sensors
US9923289B2 (en) 2014-01-16 2018-03-20 Midtronics, Inc. Battery clamp with endoskeleton design
US10473555B2 (en) 2014-07-14 2019-11-12 Midtronics, Inc. Automotive maintenance system
US10222397B2 (en) 2014-09-26 2019-03-05 Midtronics, Inc. Cable connector for electronic battery tester
US10317468B2 (en) 2015-01-26 2019-06-11 Midtronics, Inc. Alternator tester
US9966676B2 (en) 2015-09-28 2018-05-08 Midtronics, Inc. Kelvin connector adapter for storage battery
US10608353B2 (en) 2016-06-28 2020-03-31 Midtronics, Inc. Battery clamp
US11054480B2 (en) 2016-10-25 2021-07-06 Midtronics, Inc. Electrical load for electronic battery tester and electronic battery tester including such electrical load
US11513160B2 (en) 2018-11-29 2022-11-29 Midtronics, Inc. Vehicle battery maintenance device
US11566972B2 (en) 2019-07-31 2023-01-31 Midtronics, Inc. Tire tread gauge using visual indicator
US11545839B2 (en) 2019-11-05 2023-01-03 Midtronics, Inc. System for charging a series of connected batteries
US11668779B2 (en) 2019-11-11 2023-06-06 Midtronics, Inc. Hybrid and electric vehicle battery pack maintenance device
US11474153B2 (en) 2019-11-12 2022-10-18 Midtronics, Inc. Battery pack maintenance system
US11973202B2 (en) 2019-12-31 2024-04-30 Midtronics, Inc. Intelligent module interface for battery maintenance device
US11486930B2 (en) 2020-01-23 2022-11-01 Midtronics, Inc. Electronic battery tester with battery clamp storage holsters

Also Published As

Publication number Publication date
AR018748A1 (es) 2001-12-12
EP0942004A2 (fr) 1999-09-15
US20010029278A1 (en) 2001-10-11
JPH11315108A (ja) 1999-11-16
EP0942004A3 (fr) 2001-11-07
BR9902331A (pt) 2000-05-02
US6271314B1 (en) 2001-08-07
CA2265238A1 (fr) 1999-09-13
US6384150B2 (en) 2002-05-07

Similar Documents

Publication Publication Date Title
US6136914A (en) Anionic polymerization initiators for preparing macro-branched diene rubbers
EP0747405B1 (fr) Initiateurs de polymérisation comprenant un lithium-amino-magnésiate et des élastomères à basse hystérésis
EP2167557B1 (fr) Synthèse one-pot de nanoparticules et de polymère liquide pour des applications de caoutchouc
US5238893A (en) Method of preparing an anionic polymerization initiator
JP3290469B2 (ja) ゴム組成物
CA2039952C (fr) Elastomeres et produits presentant une hysteresis reduite
US5502131A (en) Method of preparing polymer using allyl-and xylyl-amine containing initiators
US5268413A (en) Elastomers and products having reduced hysteresis
US6071847A (en) Gas phase anionic polymerization of diene elastomers
US5317057A (en) (Halomethyl vinyl arene)-modified elastomers and compositions containing them having reduced hysteresis properties
JPH0660274B2 (ja) ジエン系ゴム組成物
JPS63182367A (ja) ジエン系ゴム組成物

Legal Events

Date Code Title Description
AS Assignment

Owner name: BRIDGESTONE CORPORATION, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HERGENROTHER, WILLIAM L.;COLE, WILLIAM M.;KNUTSON, THEODORE J.;AND OTHERS;REEL/FRAME:009055/0001;SIGNING DATES FROM 19980302 TO 19980308

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12